Ruthenium containing glasses and stains



March 27, 1956 P. G- HEROLD ETAL 2,739,901

RUTHENIUM CONTAINING GLASSES AND STAINS Filed July 14, 1952 80 600 20 4O 60 80 700 WAVELENGTH IN MILLIMICRONS (lNHDHHcD HONVLLIWSNVHJ.

INVENTORS:

Jfaul G- 119271111, Thegdozp y John awe lliarns,

ATTORNEYS.

United rates Patent 2,739,901 Patented Mar. 27, 19 56 using appropriate amounts of ruthenium metal, or by using appropriate amounts of any other ruthenium com- 2739 901 pound which has been comminuted and mixed through the composition. The glass, glaze, or enamel is then RUTHENIUM CONTAINING GLASSES 5 handled in an appropriate way to manufacture the de- AND STAINS sired red or black colored glass, glaze or enamel, all of Paul Herold and Theodore LM'PlanieRoHaMo which handling is a well known art in the trade. The

and John Williams, Mon-ism, N. intensity of coloration 1s controlled by the amount of ruthenium material added to the glass, glaze or enamel Application July 1952, Serial 2981308 composition, and ranges from a very light pink to a deep 6 Claims. (CL I reddish-black in compositions I,"II, IV and VI, shown 1n the table above, and ranges from a light gray to a true black in compositions III, V, and VII in the table. Composition VIII above is an example of a ceramic stain This e ti re s o the Production of red eolnfe- 15 which produces a brown coloration. The ruthenium tion and black coloration in glasses and brown coloration hi h We prefer to e i th r the iu oxid although in stains, and more particularly, to compositions containany other compound hi h may b decomposed or ing ruthenium. changed to the oxide may be used.

It is an object of this invention to make lead borosilicate The pink to reddish-black coloration achieved in the and lead Silicate glasses, glazes and enamels teke On a lead borosilicate or lead silicate glasses, glazes and pink to reddish-black Coloration by efle ed Or transenamels is produced by adding from 0.001% to 20.0% of mined light, and to make all other yp 0f glasses, glazes ruthenium, ruthenium oxide or ruthenium. oxide yielding and enamels taken on a true black coloration by reflected material, and fusing the batch so produced. or transmitted light by adding ruthenium metal or ruthe- The black color produced in the glasses, glazes and ninm OXide y other pound of ruthenium which enamels other than those of the lead borosilicate or lead Will be converted to ruthenium oxide When in intimate silicate type is what is known as a true black color, and Contact With the molten ingredients of the s, to t is characterized by an equivalent absorption of all wave batch composition of the particular glass, glaze or enamel, lengths of reflected or transmitted light. This is clearly and fusing the batch to cause the ruthenium material to illustrated by the drawing in which, it will be noted, go into solution in the melt. that the glass containing 0.075% ruthenium absorbs all A further object of this invention is to produce ceramic wave lengths of reflected or transmitted light so that the stains by mixing ruthenium containing materials with curve for this glass never rises above the zero (0) point other compounds and firing to cause a coloration in the on the ordinate. Also shown in the drawing is a curve mass of stain. for a commercial black glass of essentially the same com- The term lead borosilicate glass denotes a glass composition, in which the color is produced in the normal position produced by fusing a bath containing appreciable way; that is, by dissolving several oxides to give overlapamounts of lead oxide and boron oxide together with ping absorptions at various wave lengths. Such comsilica. mercial glass under certain conditions of use gives a The term lead silicate glass denotes a glass composireddish, bluish or greenish hue, depending on which tion produced by fusing a batch containing a predomicoloring oxide is predominant. The use of the invention, nant amount of lead oxide together with silica, which does ruthenium in solution in a glass, glaze or enamel, gives a not contain boron oxide. By a predominant amount is black coloration which imparts no predominant hue. meant that the lead oxide constituent of the batch is pres- The brown colored ceramic stain is produced by fusing ent in amounts substantially in excess of any other in- 0.005% to 20.0% ruthenium, ruthenium oxide or ruthegredient in the batch. nium oxide yielding material together with a material The accompanying drawing shows a graphical repreconsisting essentially of any one or a combination of sentation of the wave lengths of light reflected or transcompounds of elements such as silicon, titanium, germamitted by a commercial black glass in comparison with a nium, zirconium, tin, cerium, hafnium and thorium. A black glass produced by the invention. typical example is given as composition VIII in the table As examples of glasses, glazes, enamels and stains to above. which the invention may be employed, the following com- Having thus described our invention, what is claimed is: positions are given, the percentages of various com- 1. A glass composition containing from 0.001% to ounds making up a composition being expressed in per- 20.0% of a material selected from the group consisting of centages by weight. ruthenium and ruthenium oxide.

( f?) fig l (2 g) l ing n???) $10, 22. 45 17.5 70.3 28.7 59.0 31.0 42. 62 .4170 2.8 1.06 B20: 17.5 7.0 10.9 PbO 73. 91 65.0 65.0 40.8 14.70 N820 5.4 9.7 10.1 11.00 K10 3. 74 14.8 4.0 as 10.1 2.50 CaO 2.0 8.7 1.20 MgO 2.29 E50 2.3 ZnO 1.10 81102.- 8.0 513201 0.20 F1. 3. 94 Tiol 99.9 R110, 0. 003 0. 003 0.075 0.003 0. 075 0. 003 0.075 0.1

Proper coloration may be produced in any of the typical glasses, glazes and enamels given in the above table by using appropriate amounts of a salt of ruthenium or by 2. A pink to reddish-black colored glass, glaze and enamel which consists essentially of a glass composition selected from the group consisting of lead borosilicate glasses. and lead silicate classes, and from 000.1% to 20.0% of a material selected from the group consisting of ruthenium and ruthenium-oxide.

A brown-colored ce amic stain onsist ng ess ntial- 1y of at. least one oxide selected trom the g up nsistingzof titanium and zirconium oxides, and from 0.005% to 20.0% of a'imaterial selected from the group consisting of ruthenium and ruthenium oxide.

-4. Astaiu as recited in claim 3 in which the oxide is titanium oxide. 7

5. A method of producing a pink to reddish-black coloration in glasses, glazes and enamels which compri e ad g o the batch composition of a glass selected from the :group consisting of lead horosilicate glasses andleadisilicate glasses from 0.001% to 20.0%

.ot a. material selected .fmm the .zcoup consisting of .(.1.)

ruthenium, (2) ruthenium oxide, and (3) compounds of ruthenium which will be converted to ruthenium oxide when in intimate contact with the molten ingredients of the glass to be colored, and then subjecting the batch composition to suflicient .heat .to cause fusion.

6. A method of producing a brown-colored ceramic stain which comprises, fusing together at leastone oxide selected from the group consisting of titanium and zirconium oxides and -from 0.005 to 20.0% of a material selected from the group consisting of (1) ruthenium, (2)

No references cited. 

1. A GLASS COMPOSITION CONTAINING FROM 0.001% TO 20.0% OF A MATERIAL SELECTED FROM THE GROUP CONSISTING RUTHENIUM AND RUTHENIUM OXIDE. 